Asian Journal of Chemistry; Vol. 25, No. 8 (2013), 4401-4403
http://dx.doi.org/10.14233/ajchem.2013.13992
Synthesis, Crystal Structure and Antitumor Activity of 1D Coordination
Polymer of Ca(II) and Na(I) with N-p-tolylsulfonyl-glycine
TAI XI-SHI* and LI FA-HUI
College of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, P.R. China
*Corresponding author: Fax: +86 536 8785363; Tel: +86 536 8785363; E-mail: [email protected]; [email protected]
(Received: 30 April 2012;
Accepted: 11 February 2013)
AJC-12974
1D coordination polymer formed by Ca(II) and Na(I) was synthesized by the reaction of calcium perchlorate, NaOH with N-p-tolylsulfonylglycine in the CH3CH2OH/H2O (v:v = 3:1). It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis.
The crystal of the complex belongs to triclinic, space group P-1 with a = 0.95657(10) nm, b = 1.09171(11) nm, c = 1.8292(2) nm, α =
80.6790(10)º, β = 86.831(2)º, γ = 89.957(2)º, V = 1.8821(3) nm3, Z = 2, Dc = 1.599 Mg m-3, µ = 0.507 mm-1, F(000) = 936 and final R1 =
0.0981, wR2 = 0.2262. The complex comprises a seven-coordinated Ca(II) center, with a O7 distorted pengonal coordination environment
and a six-coordinated Na(I) center, with distorted octahedron environment. The molecules are connected by the oxygen atoms of carboxylates
to form one dimensional chain structure. The antitumor activities against gastric cancer cells of free ligand and its Ca(II) complex were
studied by MTT method.
Key Words: N-p-Tolysulfonyl-glycine, Ca(II) complex, Synthesis, Crystal structure, Antitumor activity.
INTRODUCTION
In recent years, coordination polymers have attracted
much attention owing to their enormous variety of interesting
framework topologies and their wide range of potential
applications in adsorption, separation, catalysis, biological
property and luminescence1-3. To data, a large number of
coordination polymers assembled from carboxylates and
transition metals have been extensively investigated4,5. However, the coordination polymers of Ca(II) with carboxylates
have rarely been studied due to the low coordination ability of
Ca(II)6. So it is essential to design appropriate ligands to form
the stable Ca(II) complex. In this paper, we report the synthesis
and X-ray crystal structure of 1D coordination polymer formed
by Ca(II) and Na(I). The antitumor activities against gastric
cancer cells of free ligand and its Ca(II) complex were studied
by MTT method.
EXPERIMENTAL
The following A.R. grade chemicals were used for the
preparation of the studied compound e.g., calcium perchlorate,
p-tolysulfonyl chloride, glycine, sodium hydroxide.
The carbon, hydrogen and nitrogen content in the newly
synthesized compound were determined on a Elementar Vario
III EL elemental analyzer. Infrared spectrum (4000-400 cm-1)
was recorded with KBr optics on a Nicolet AVATAR 360 FTIR
spectrophotometer. The crystal data was collected on a Bruker
smart CCD Area Detector.
Synthesis of the ligand: 10 mmol (0.7507 g) of glycine
and 20 mmol (0.8 g) of sodium hydroxide were dissolved in
100 mL of water at room temperature and added drop by drop
10 mmol (1.9065 g) of p-tolylsulfonyl chloride by stirring at
room temperature. The reaction solution was kept running for
4 h, then acidified with the solution of hydrochloric acid (V:V
= 1:1) to pH = 2. The white solid precipitation were collected
by filtration, washed and dried under vacuum (Fig. 1). Yield
may reach up to over 65 %. Elementary analysis: calcd. (%)
for C9H11NSO4: C, 47.16; H, 4.80; N, 6.11; found (%): C, 47.58;
H, 4.52; N, 6.39. IR (KBr, νmax, cm-1): (C=O): 1719, (N-H): 3248.
Synthesis of Ca(II) complex: 1 mmol of N-p-tolylsulfonyl-glycine and 1 mmol (0.04 g) of sodium hydroxide
were added to the 10 mL of C2H5OH/H2O (v:v = 3:1) solution.
After being dissolved, 0.5 mmol of calcium perchlorate was
added to the solution. The mixture was continuously stirred
for 3 h at refluxing temperature. The mixture was cooled at
room temperature and was collected by filtration. By evaporation in air at room temperature, the single crystal suitable
for X-ray determination was obtained from methanol solution
after 15 days. Yield: 57 %. Elementary analysis: calcd. (%)
for C27H34N3O18S3ClCaNa2: C, 35.75; H, 3.75; N, 4.63; found
(%): C, 35.58; H, 3.49; N, 4.72. IR (KBr, νmax, cm-1): (C=O):
1680, (N-H): 3247, (H2O): 3428, (Ca-O): 418.
4402 Xi-Shi et al.
X-Ray crystallography: A colourless block single crystal
with dimensions of 0.48 mm × 0.47 mm × 0.23 mm was placed
on a glass fiber and mounted on a CCD area detector. Diffraction data were collected by φ~ω scan mode using a graphitemonochromatic MoKα radiation (λ = 0.71073 Å) at 293(2) K.
A total of 9043 reflections were collected in the range 2.0425.01º, of which 6031 were unique (Rint = 0.0523) and 4640
were observed with I > 2σ(I). The data were corrected for Lp
factors. The structure was solved by direct methods and
refined by full-matrix least-squares techniques on F2. The
structure was solved by direct methods7 using SHELXL-97
and expanded using Fourier techniques. All non-hydrogen
atoms and hydrogen atoms were refined anisotropically and
isotropically, respectively. The final refinement by fullmatrix least squares method was converged at R = 0.0981 and
wR = 0.2262 (w = 1/[δ2(Fo2) + (0.1064P)2 + 11.3326P], P =
(Fo2 + 2Fc2)/3, S = 1.040, (∆/σ)max = 0.001). The largest peak
in the final difference Fourier map is 0.812 e/Å3 and the
minimum peak is -0.487 e/Å3. Molecular graphics were drawn
with the program package SHELXTL-97 crystallographic
software package8. The most relevant crystal data for complex
are presented in Table-1 and the selected bond distances and
angles are listed in Table-2.
TABLE-1
CRYSTALLOGRAPHIC DATA FOR Ca(II) COMPLEX
Formula
C27H34N3O18S3ClCaNa2
Formula weight
906.26
Crystal system
Triclinic
Space group
P-1
a (Å)
9.5657(10)
b (Å)
10.9171(11)
c (Å)
18.292(2)
80.6790(10)
α (º)
86.831(2)
β (º)
89.957(2)
γ (º)
Z
2
F(000)
936
Temperature (K)
293(2)
V (Å3)
1882.1(3)
Calculated density (g cm-3)
1.599
Crystal size (mm3)
0.48 × 0.47 × 0.23
µ (mm-1)
0.507
Limiting indices
-10 ≤ h ≤ 11, -11 ≤ k ≤ 12, -13
≤ l ≤ 21
Reflections collected
9043
Reflections unique
6031
R1, wR2 [all data]
0.1187, 0.2391
0.0981, 0.2262
R1, wR2 [I > 2σ(I)]
Largest diff. peak and hole (e Å-3)
0.812, -0.487
Antitumor activity: Gastric cancer cells were propagated
continuously in culture and grown in RPMI 1640 medium with
10 % inactivated fetal calf serum and antibiotics. Cell harvested
from exponential phase were seeded equivalently into 96 well
plates and incubated for 24 h, then compounds studied were
added in a concentration gradient. The final concentrations
were maintained at c/(µg mL-1) 5, 10, 20, respectively. The
plates were maintained at 37 ºC in a humidified 5 % CO2-90
% N2-5 % O2 atmosphere and incubated for 48 h, the MTT
solution was added, the following procedure referred to10. The
Asian J. Chem.
TABLE-2
SELECTED BOND LENGTHS (Å)
AND ANGLES (º) FOR Ca(II) COMPLEX
Ca1-O9
2.375(5)
Na1-O7
2.40(2)
Ca1i-O10
2.442(4)
Na1iii-O11
2.416(5)
Ca1ii-O1
2.470(5)
Na1ii-O1
2.433(5)
Ca1-O14
2.496(5)
Na1i-O10
2.512(6)
Ca1-O6
2.534(5)
Na2iv-O4
2.324(6)
Ca1-O13
2.568(5)
Na2v-O12
2.325(5)
Ca1-O5
2.588(5)
Na2i-O10
2.339(5)
Ca1i-O19
3.231(6)
Na2-O13
2.435(6)
Na1-O3
2.347(6)
Na2ii-O1
2.445(5)
Na1-O5
2.375(5)
Na2iii-O11
2.521(6)
N1-C2
1.414(9)
N2-S2
1.619(7)
N1-S1
1.597(5)
N3-S3
1.585(5)
N2-C11
1.453(11)
–
–
O2i-Ca1-O9
91.21(18)
O2i-Ca1-O14
81.34(19)
O2i-Ca1-O10i
151.75(19)
O9-Ca1-O14
67.78(18)
O9-Ca1-O10i
105.95(16)
O10i-Ca1-O14
84.60(18)
O2i-Ca1-O1ii
107.88(17)
O1ii-Ca1-O14
141.14(18)
O9-Ca1-O1ii
146.12(19)
O2ii-Ca1-O6
76.20(19)
i
ii
O10 -Ca1-O1
69.65(15)
O3-Na1-O5
114.3(2)
O3-Na1-O7
79(3)
O14-Ca1-O6
137.71(18)
O5-Na1-O7
84(4)
O2i-Ca1-O13
76.91(18)
O3-Na1-O1ii
154.3(2)
O9-Ca1-O13
140.88(18)
O5-Na1-O1ii
75.83(17)
O10i-Ca1-O13
75.66(16)
ii
O7-Na1-O1
127(3)
O1i-Ca1-O13
72.16(16)
O3-Na1-O10i
88.30(19)
O14-Ca1-O13
73.59(17)
O11-Na2-O13i
80.15(18)
O6-Ca1-O13
132.98(17)
O13-Na2-O1ii
74.90(18)
O2ii-Ca1-O5
127.16(18)
O9-Ca1-O6
77.27(17)
O9-Ca1-O5
74.71(18)
O10i-Ca1-O6
128.83(17)
O10-Ca1-O5
79.77(16)
O1ii-Ca1-O6
80.43(15)
O1ii-Ca1-O5
71.45(15)
–
–
O14-Ca1-O5
133.24(17)
–
–
O6-Ca1-O5
51.17(16)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) x, y-1, z; (iv)
-x+1, -y, -z+1; (v) -x+2, -y+1, -z+1.
measurements of absorption of the solution concerned with
the number of live cells were performed on spectrophotometer
at 570 nm.
RESULTS AND DISCUSSION
IR Spectra: The free ligand exhibits characteristic the
COOH stretching band at 1719 and 1436 cm-1, which appeared
at at 1718 cm-1 was assigned as νas(COO–) and that at 1435
cm-1 as νs(COO–) in the complex, the lower shifting of COO–
stretching frequency verify the coordination of the carboxylate
oxygen atoms with Ca(II) ion10. The -SO2- stretching frequency
occurs at 1336 and 1201 cm-1, whereas for the complex which
appears at 1288 and 1176 cm-1. The -SO2- stretching frequency
is shifted to a lower frequency, suggesting that the Na-O bands
are formed between the Na ion and oxygen atoms of -SO2groups. In addition, the band at 3426 cm-1 shows that the
complex contains water molecules, which are accordance with
the results of elemental analysis.
H3 C
O
S
Cl+
H2 N
COOH
O
O
H3 C
S
O
Fig. 1. Synthesis of ligand
H
N
COOH
Vol. 25, No. 8 (2013)
Synthesis and Antitumor Activity of 1D Coordination Polymer of Ca(II) and Na(I) 4403
Structure description: Perspective view of the molecule
in a unit cell and molecular packing arrangement are shown
in Figs. 2 and 3, respectively. It can be seen that the coordination
environment of the Ca(II) atom consists of eight oxygen atoms
from the coordinated water molecules and N-p-tolysulfonylglycinate ligand, making up a distorted pseudo square
antiprismatic environment. In the complex molecule, it consists
of two different Na ions. Na1 is coordinated by six oxygen
atoms from the carboxylatos and S=O groups of N-p-tolysulfonylglycinate ligand, making up a distorted octahedral environment.
Na2 is coordinated by five oxygen atoms from the carboxylatos
and S=O groups of N-p-tolysulfonyl-glycinate ligand and one
oxygen atom from the coordinated water molecules, also making
up a distorted octahedral environment. The distances of the
Ca(1)-O bonds are in the range of 2.293(5)-2.588(5) Å, which
are similar to the Ca-O bond lengths reported previously11-13.
The distances of the Na(1)-O bonds are in the range of
2.347(6)-2.512(6) Å and that of Na (2)-O bonds are in the
range of 2.324(6)-2.521(6) Å, respectively.
Fig. 4. One dimensional chained structure of complex
H13B···O6, 2.827 (7) Å, symmetry code: 2-x, 2-y, 1-z; O14H14B···O5, 2.883 (7) Å, symmetry code: 1-x, 1-y, 1-z.
Antibacterial activity: The data of the antitumor activities
of Ca(II) complex and ligand are given in Table-3. The concentration of DMSO was controlled under 1 % to assure not to
affect the results14. As can be seen, the inhibitory rates of Ca(II)
complex against gastric cancer cells increased with increasing
of dose. The inhibitory effects of Ca(II) complex are higher
than that of ligand.
TABLE-3
ANTITUMOR ACTIVITY OF AGAINST
GASTRIC CANCER CELLS
Compound
Dose (µg mL-1)
Inhibitory rate (%)
5.0
16.0
Ca(II) complex
10.0
23.48
20.0
32.99
5.0
11.50
N-p-Tolylsulfonyl-glycine
10.0
18.93
20.0
24.70
ACKNOWLEDGEMENTS
Fig. 2. Molecular structure of the complex, where the thermal ellipsoids
were drawn at 30 % possibility
The authors thank the National Natural Science Foundation
of China (No. 21171132 and 20671073), the Promotive
Research Fund for Excellent Young and Middle-aged Scientisits
of Shandong Province (2010BSA07004) and Science Foundation of Weifang University.
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Fig. 3. Packing of the complex in the unit cell
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